CN103910606B - Ethynylation condensation method is produced 2,5-dimethyl-2, the method for 5-hexylene glycol - Google Patents
Ethynylation condensation method is produced 2,5-dimethyl-2, the method for 5-hexylene glycol Download PDFInfo
- Publication number
- CN103910606B CN103910606B CN201310285157.9A CN201310285157A CN103910606B CN 103910606 B CN103910606 B CN 103910606B CN 201310285157 A CN201310285157 A CN 201310285157A CN 103910606 B CN103910606 B CN 103910606B
- Authority
- CN
- China
- Prior art keywords
- potassium hydroxide
- aqueous solution
- dimethyl
- ethynylation
- hexylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a kind of ethynylation condensation method and produce 2,5-dimethyl-2, the method for 5-hexylene glycol, the method comprises the following steps: 1. make the feed liquid containing hexin glycol taking acetylene and acetone as raw material; 2. potassium hydroxide separating still separates; 3. potassium hydroxide aqueous solution is sent into nickel alloy continuous evaporator and carried out distillation and concentration potassium hydroxide aqueous solution; 4. the potassium hydroxide solution after concentrated is sent into inorganic impurity separator, remove organic impurities; 5. the potassium hydroxide aqueous solution after removal of impurities is sent into cast iron evaporimeter, evaporating water, becomes solid state hydrogen potassium oxide; Continuous heating again, makes solid state hydrogen potassium oxide become molten state, then naturally cooling, makes its crystallization again; 7. with slicer, the potassium hydroxide of crystallization is again cut into slices, as catalyst raw material, recycle. Compared with the existing, the present invention recycles potassium hydroxide, thereby provides cost savings.
Description
Technical field
The present invention relates to ethynylation condensation method and produce 2,5-dimethyl-2,5-hexylene glycol, particularly ethynylation condensation method is produced 2,5-dimethyl-2, the method for 5-hexylene glycol.
Background technology
Domestic product 2,5-dimethyl-2, the enterprise of 5-hexylene glycol is little, and it is domestic that main scale enterprise is distributed in Sichuan Province's Luzhou City, comprises Luzhou Xin Fu Chemical Co., Ltd. (the wholly-owned holding company of this enterprise), produces 5,000 tons per year; Luzhou Fu Bang chemical company, produces 2,000 tons per year; Luzhou Rui Xing chemical company, produces 1200 tons per year. Also have other enterprises of minority to produce this product as Yibin, Sichuan Heng De Chemical Co., Ltd., but scale is less.
Domestic enterprise is mainly taking benzene as solvent, potassium hydroxide is made catalyst, by acetylene and acetone, to be primary raw material carry out ethynylation condensation reaction under normal pressure and certain temperature conditions makes the intermediate product hexin glycol of DHAG (2,5-dimethyl-2,5-hexylene glycol). In process of production, the consumption maximum of potassium hydroxide, the potassium hydroxide consumption of 1 ton of DHAG of every production is 1.13 tons, nearly 10,000 yuan of cost. Potassium hydroxide has just formed the aqueous solution in technical process, has become refuse.
In domestic prior art, adopt hydrochloric acid directly in and potassium hydroxide aqueous solution, can waste a large amount of hydrochloric acid and potassium hydroxide (mol ratio is 1: 1), finally also need the moisture in heating evaporation neutralization reaction product, time consumption and energy consumption; Or be sold to potash manufacturing enterprise using potassium hydroxide aqueous solution as refuse, its selling price is very low.
A large amount of potassium hydroxide of how sneaking in processing reaction product, be cost-saving, increase the benefit and reduce the key issue of refuse. And go together at home in enterprise, not yet carry out recycle and reuse technical research and the exploitation of potassium hydroxide, have a strong impact on economic benefit and the sustainable development of enterprise.
Summary of the invention
Object of the present invention is just to provide a kind of ethynylation condensation method to produce 2,5-dimethyl-2, the method for 5-hexylene glycol, and this ethynylation condensation method is produced 2,5-dimethyl-2, and the method for 5-hexylene glycol recycles potassium hydroxide, thereby provides cost savings.
Technical scheme of the present invention is: a kind of ethynylation condensation method produces 2,5-dimethyl-2, the method of 5-hexylene glycol, the method comprises the following steps: 1. taking acetylene and acetone as raw material, taking benzene as solvent, taking potassium hydroxide as catalyst, under nitrogen protection condition, react, make the feed liquid containing hexin glycol;
2. add clear water washing, after washing, feed liquid is pressed to people's potassium hydroxide separating still, stratification, utilizes density difference principle, makes highdensity potassium hydroxide aqueous solution be deposited on lower floor; Low-density hexin glycol benzole soln is suspended in upper strata; Potassium hydroxide aqueous solution is put into alkali lye storage tank at the bottom of potassium hydroxide separating still still, and remaining hexin glycol benzole soln continues subsequent technique and produces 2,5-dimethyl-2,5-hexylene glycol;
3. potassium hydroxide aqueous solution is sent into nickel alloy continuous evaporator and carried out distillation and concentration potassium hydroxide aqueous solution;
4. the potassium hydroxide solution after concentrated is sent into inorganic impurity separator, remove organic impurities;
5. the potassium hydroxide aqueous solution after removal of impurities is sent into cast iron evaporimeter, evaporating water, becomes solid state hydrogen potassium oxide; Continuous heating again, makes solid state hydrogen potassium oxide become molten state, then naturally cooling, makes its crystallization again;
7. with slicer, the potassium hydroxide of crystallization is again cut into slices, as catalyst raw material, recycle.
As preferably; described step detailed step is 1.: first benzene, potassium hydroxide are dropped in reactor; stir, pass into nitrogen protection, then add acetylene; reactor pressure is controlled at 0.35MPa; when temperature of reaction kettle is raised to 45 DEG C, slowly evenly drip acetone, react, reaction temperature is controlled at 43-47 DEG C; stop adding after acetone pressurize 2 hours, react fully thoroughly.
As preferably, described inorganic impurity separator is a hydraulic cyclone group device.
As preferably, described potassium hydroxide separating still comprises storage tank groove body, and this storage tank body is connected with alkali lye the first blow-off valve, and the described alkali lye first blow-off valve other end connects a N-shaped device, and this N-shaped device other end connects alkali lye second blow-off valve.
As preferably, described N-shaped device is a N-shaped pipeline, and N-shaped duct height is 500mm.
Compared with prior art, beneficial effect of the present invention is: utilize the immiscible feature of potassium hydroxide aqueous solution and benzene, after having reacted, enter potassium hydroxide separating still and leave standstill, after leaving standstill, upper solution is the benzole soln containing hexin glycol, and lower floor is the potassium hydroxide mixed solution that contains high concentration. Potassium hydroxide mixed solution after separation enters inorganic impurity separator after utilizing the organic different boiling temperature such as acetone, benzene, acetylenic glycols intermediate product to distill in nickel alloy continuous evaporator inorganic impurity is separated, then enter cast iron evaporimeter heating moisture is evaporated and make alkali fusion after enter drum-type slicing machine and carry out trimming. Adopt this method to neutralize without hydrochloric acid, and catalysts potassium hydroxide can recycle. By the present invention, rear approximately more than 70% potassium hydroxide of recovery directly returns to reactor and reacts next time, thereby has effectively saved cost.
Brief description of the drawings
Fig. 1 is process chart of the present invention;
Fig. 2 is potassium hydroxide separating still structural representation of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, the invention will be further described.
Ethynylation condensation method is as shown in Figure 1 produced 2,5-dimethyl-2, the method for 5-hexylene glycol, and the method comprises the following steps: 1. reaction generates intermediate product hexin glycol step; In reactor 13, drop into benzene, potassium hydroxide, stir, then pass into nitrogen 60 minutes, add acetylene, reactor pressure is controlled at 0.08MPa, slowly evenly adds acetone when temperature of reaction kettle is raised to 45 DEG C, reaction temperature is controlled at 43-47 DEG C, stops adding after acetone pressurize 2 hours, and washing then adds water;
2. after washing, feed liquid is pressed to people's potassium hydroxide separating still 1, stratification, the potassium hydroxide mixed solution that contains high concentration after layering is put into alkali lye storage tank 2 from potassium hydroxide separating still 1 bottom by pipeline; As shown in Figure 2, potassium hydroxide separating still 1 comprises storage tank groove body 11, and this storage tank body 11 is connected with alkali lye the first blow-off valve 12, and alkali lye first blow-off valve 12 other ends connect a N-shaped device 13, and these N-shaped device 13 other ends connect alkali lye the second blow-off valve 14. N-shaped device 13 is a N-shaped pipeline, and N-shaped duct height is 500mm. While discharge like this, organic solvent and accessory substance remain at N-shaped device height and can not drain with alkali lye layer, therefore recycle by the potassium hydroxide aqueous solution of discharging lower floor, and the organic solvent on upper strata reclaims and uses, thereby reach the effect of separation.
3. mix to dissolve into into nickel alloy continuous evaporator 4 from alkali lye storage tank 2 potassium hydroxide out and distill, vapo(u)rizing temperature is controlled at 80-100 DEG C;
4. from nickel alloy continuous evaporator 4 bottoms potassium hydroxide solution out enter inorganic impurity separator 6 carry out normal temperature cooling separation;
5. after entering pretreatment alkali lye storage tank 9, inorganic impurity separator 6 potassium hydroxide solution after treatment enters again intermediate storage tank 10;
6. from intermediate storage tank, 10 potassium hydroxide solutions out enter in cast iron evaporimeter 11 and heat high alkali liquid, moisture is evaporated and make alkali fusion, then adopt drum-type slicing machine 12 to cut into slices, the potassium hydroxide of weighing to obtain;
7. the potassium hydroxide obtaining in is 6. returned and in reactor 13, generate the reaction of intermediate product hexin glycol next time.
Experiment 1
In reactor 13, drop into 8.2 tons of benzene, 0.9 ton, potassium hydroxide, stir, then pass into nitrogen 60 minutes (nitrogen pass into speed be 65 milliliters per minute), add 0.23 ton of acetylene, reactor 13 pressure are controlled at 0.08MPa, slowly evenly add 0.885 ton, acetone (feed time is 5 ± 2 hours) when reactor 13 temperature are raised to 45 DEG C, and reaction temperature is controlled at 45 ± 2 DEG C, stop adding after acetone pressurize 2 hours, washing then adds water.
After washing, feed liquid is pressed to people's potassium hydroxide separating still 1, stratification. The potassium hydroxide mixed solution that contains high concentration after layering is put into alkali lye storage tank 2 from potassium hydroxide separating still 1 bottom by pipeline, out enter once concentration cover still (not drawing Fig. 1) from top containing the feed liquid of acetylenic glycols and carry out next step operation, process is below with existing identical, finally produce 2,5-dimethyl-2,0.8 ton of 5-hexylene glycol.
Mix to dissolve into into nickel alloy continuous evaporator 4 from alkali lye storage tank 2 potassium hydroxide out and distill, vapo(u)rizing temperature is controlled at 80-100 DEG C, enters and reclaims measuring tank 7 from nickel alloy continuous evaporator 4 tops gas out after shell and tube condenser 3. From the liquid out of nickel alloy continuous evaporator 4 bottoms, concentration of potassium hydroxide reaches 42 ~ 45%.
From nickel alloy continuous evaporator 4 bottoms potassium hydroxide solution out enter inorganic impurity separator 6 carry out normal temperature cooling water revolve separation, inorganic impurity separator 6 is a hydraulic cyclone group device.
After entering pretreatment alkali lye storage tank 9, inorganic impurity separator 6 potassium hydroxide solution after treatment enters again intermediate storage tank 10.
From intermediate storage tank 10, potassium hydroxide solution out enters cast iron evaporimeter 11(and is also natural gas solid caustic soda pot) in heating high alkali liquid, moisture is evaporated and make alkali fusion, then adopt drum-type slicing machine 12(to be also sheet alkali slicer) weigh after the cooling section of discharging, potassium hydroxide (removing the moisture content that potassium hydroxide absorbs when cooling) weighs 0.81 ton, after testing, this potassium hydroxide is as broad as long with technical grade potassium hydroxide (potassium hydroxide adding while reaction above) various aspects of performance.
The potassium hydroxide of acquisition is returned and in reactor 13, generates the reaction of intermediate product hexin glycol next time.
Claims (5)
1. an ethynylation condensation method is produced 2,5-dimethyl-2, and the method for 5-hexylene glycol, is characterized in that the method comprises the following steps:
1. taking acetylene and acetone as raw material, taking benzene as solvent, taking potassium hydroxide as catalyst, under nitrogen protection condition, in reactor, react, make the feed liquid containing hexin glycol;
2. add clear water washing, the feed liquid after washing is pressed into potassium hydroxide separating still, stratification, utilizes density difference principle, makes highdensity potassium hydroxide aqueous solution be deposited on lower floor; Low-density hexin glycol benzole soln is suspended in upper strata; Potassium hydroxide aqueous solution is put into alkali lye storage tank at the bottom of potassium hydroxide separating still still, and remaining hexin glycol benzole soln continues subsequent technique and produces 2,5-dimethyl-2,5-hexylene glycol;
3. potassium hydroxide aqueous solution is sent into nickel alloy continuous evaporator and distilled, concentrated potassium hydroxide aqueous solution;
4. the potassium hydroxide aqueous solution after concentrated is sent into inorganic impurity separator, remove organic impurities;
5. the potassium hydroxide aqueous solution after removal of impurities is sent into cast iron evaporimeter, evaporating water, becomes solid state hydrogen potassium oxide; Continuous heating again, makes solid state hydrogen potassium oxide become molten state, then naturally cooling, makes its crystallization again;
6. with slicer, the potassium hydroxide of crystallization is again cut into slices, as catalyst raw material, recycle.
2. ethynylation condensation method according to claim 1 is produced 2,5-dimethyl-2, the method for 5-hexylene glycol; it is characterized in that: described step detailed step is 1.: first benzene, potassium hydroxide are dropped in reactor; stir, pass into nitrogen protection, then add acetylene; reactor pressure is controlled at 0.35MPa; when temperature of reaction kettle is raised to 45 DEG C, slowly evenly drip acetone, react, reaction temperature is controlled at 43-47 DEG C; stop adding after acetone pressurize 2 hours, react fully thoroughly.
3. ethynylation condensation method according to claim 1 is produced 2,5-dimethyl-2, and the method for 5-hexylene glycol, is characterized in that: described inorganic impurity separator is a hydraulic cyclone group device.
4. ethynylation condensation method according to claim 1 produces 2,5-dimethyl-2, the method of 5-hexylene glycol, it is characterized in that: described potassium hydroxide separating still comprises storage tank groove body, this storage tank body is connected with alkali lye the first blow-off valve, the described alkali lye first blow-off valve other end connects a N-shaped device, and this N-shaped device other end connects alkali lye the second blow-off valve.
5. ethynylation condensation method according to claim 4 is produced 2,5-dimethyl-2, and the method for 5-hexylene glycol, is characterized in that: described N-shaped device is a N-shaped pipeline, and N-shaped duct height is 500mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310285157.9A CN103910606B (en) | 2013-07-09 | 2013-07-09 | Ethynylation condensation method is produced 2,5-dimethyl-2, the method for 5-hexylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310285157.9A CN103910606B (en) | 2013-07-09 | 2013-07-09 | Ethynylation condensation method is produced 2,5-dimethyl-2, the method for 5-hexylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103910606A CN103910606A (en) | 2014-07-09 |
| CN103910606B true CN103910606B (en) | 2016-05-25 |
Family
ID=51036658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310285157.9A Active CN103910606B (en) | 2013-07-09 | 2013-07-09 | Ethynylation condensation method is produced 2,5-dimethyl-2, the method for 5-hexylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103910606B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317124A (en) * | 2019-06-20 | 2019-10-11 | 袁玮 | The technique that environmental protection treatment produces the industrial residu that alkynes alcoholic product generates and waste coke oil |
| CN110511113A (en) * | 2019-08-16 | 2019-11-29 | 袁玮 | The technique of batch process coproduction alkynol and alkanol and by-product inorganic salts |
| CN110540489B (en) * | 2019-09-17 | 2022-09-02 | 凯莱英生命科学技术(天津)有限公司 | Method for addition reaction of acetylene and ketone compound |
| CN111268696B (en) * | 2020-03-10 | 2022-09-09 | 四川众邦新材料股份有限公司 | Method for treating waste potassium hydroxide solution in alkynol production |
| CN111790172A (en) * | 2020-07-29 | 2020-10-20 | 濮阳市盛源能源科技股份有限公司 | Solvent distillation recovery system and use method |
| CN115228144A (en) * | 2022-07-28 | 2022-10-25 | 重庆鑫盛通化工有限公司 | Device and method for recovering potassium hydroxide in production of 2, 5-dimethyl-2, 5-hexanediol |
| CN115894172A (en) * | 2022-10-14 | 2023-04-04 | 青岛科技大学 | Continuous production system and method of 2, 5-dimethyl-2, 5-hexanediol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247181A (en) * | 1999-08-25 | 2000-03-15 | 成都惟精防水材料研究所 | One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol |
| CN101234950A (en) * | 2008-02-02 | 2008-08-06 | 泸州富邦化工有限公司 | Technique for producing 2,5-dimethyl-2,5-hexandiol by extraction and decompression distillation method |
-
2013
- 2013-07-09 CN CN201310285157.9A patent/CN103910606B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247181A (en) * | 1999-08-25 | 2000-03-15 | 成都惟精防水材料研究所 | One-step synthesizing process of 2,5-dimethyl-2,5-hexanediol |
| CN101234950A (en) * | 2008-02-02 | 2008-08-06 | 泸州富邦化工有限公司 | Technique for producing 2,5-dimethyl-2,5-hexandiol by extraction and decompression distillation method |
Non-Patent Citations (2)
| Title |
|---|
| 己二醇合成工艺的改进;高远明;《四川化工》;19971231(第4期);24-27 * |
| 氢氧化钾片碱生产中的节能降耗;乔治库;《中国氯碱》;20090331(第3期);40-41 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103910606A (en) | 2014-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103910606B (en) | Ethynylation condensation method is produced 2,5-dimethyl-2, the method for 5-hexylene glycol | |
| CN101906355A (en) | Method for preparing biodiesel by utilizing food waste recycling oil | |
| CN101955211A (en) | Method for extracting lithium carbonate from lepidolite | |
| CN102021082A (en) | Method for preparing fatty acid methyl ester and glycerol from kitchen waste oil by utilizing acid-base two-step method | |
| CN108129445A (en) | The method that formaldehyde prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying | |
| CN104818125A (en) | Method for using waste oil and grease as raw material to prepare fatty acid methyl ester | |
| CN105111246A (en) | Method for recycling organic tin in sucralose production | |
| CN102850519A (en) | Synthetic method of epoxy resin, and associated device thereof | |
| CN109593540B (en) | Method for separating phenolic compounds from coal tar | |
| CN101518747A (en) | Recycling system of chlorination mother solution and recycling method thereof | |
| CN106831334A (en) | A kind of continuous production processes of alkaline process petrohol potassium | |
| CN103540414B (en) | The method and apparatus of a kind of palm dregs of fat and acidification oil refining biofuel | |
| CN111848326A (en) | Industrial treatment method for recycling pentamethyl indane | |
| CN104844469A (en) | Clean production technology of methyl anthranilate | |
| CN102513132A (en) | Dedicated DYD catalyst for one-step bio-diesel production and production method thereof | |
| CN102701908A (en) | Process for preparing neopentyl glycol with calcium method | |
| CN102504852B (en) | Improved Litwin coal tar processing technic | |
| CN102001655A (en) | Method for cleaning and recovering activating agent in production process of activated carbon | |
| CN103936041B (en) | A kind of recoverying and utilizing method containing aluminium Waste Sulfuric Acid | |
| CN103721749B (en) | Avoid composite catalyst and the application thereof of fouling in production of biodiesel | |
| CN103642010B (en) | A kind of method utilizing recovery alcohol to prepare hexanodioic acid kind polyester polyvalent alcohol | |
| CN202705267U (en) | Glycol dimethyl ether component recovery device in synthetic product waste salt | |
| CN112409174A (en) | Preparation device and method of 3, 3-methyl dimethacrylate | |
| CN102887525B (en) | Method for making boric acid by using boromagnesite | |
| CN105037078A (en) | Method for recovering dichloromethane in chlorone mother liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Lai Dajun Inventor after: Nie Yong Inventor after: Yang Tingquan Inventor before: Nie Yong |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: NIE YONG TO: LAI DAJUN NIE YONG YANG TINGQUAN |
|
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Nie Yong Inventor after: Lai Dajun Inventor after: Yang Tingquan Inventor after: Chen Dexu Inventor before: Lai Dajun Inventor before: Nie Yong Inventor before: Yang Tingquan |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: LAI DAJUN NIE YONG YANG TINGQUAN TO: NIE YONG LAI DAJUN YANG TINGQUAN CHENDEXU |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |